CN101774777B - Preparation method of calcium oxide expansion agents - Google Patents
Preparation method of calcium oxide expansion agents Download PDFInfo
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- CN101774777B CN101774777B CN2010101015203A CN201010101520A CN101774777B CN 101774777 B CN101774777 B CN 101774777B CN 2010101015203 A CN2010101015203 A CN 2010101015203A CN 201010101520 A CN201010101520 A CN 201010101520A CN 101774777 B CN101774777 B CN 101774777B
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- calcium oxide
- expansion agents
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- oxide expansion
- expansion
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a preparation method of calcium oxide expansion agents. The method comprises the following steps: mixing and grinding lime stone and composite mineralizer to obtain raw material, calcining at 1100-1300 DEG C to obtain calcium oxide expansion agent chamotte, and mixing and grinding the chamotte with disperse carrier to obtain the calcium oxide expansion agents, wherein composite mineralizer is composed of 50-70wt% of gypsum and 30-50wt% of copper slag, the weight ratio of composite mineralizer to lime stone is 5:95-10:90, and the weight ratio of calcium oxide expansion agent chamotte to disperse carrier is 75:25-90:10. The calcining heat of the calcium oxide expansion agents of the invention is relatively lower, calcium oxide is not easy to overheat; the water requirement of hydrated product is small, the expansion efficiency is high, the expansion rate is high; and cement concrete can realize effective expansion in dry environment.
Description
Technical field
The present invention relates to a kind of preparation method of calcium oxide expansion agents.
Background technology
Since France's invention thirties in 20th century expansive cement; Particularly on the basis of Japan, expansion component has wherein been separated since the swelling agent as independent admixture at expansive cement; Cement expansive material develops into one of admixture of consumption maximum in the concrete industry gradually; Be widely used in underground waterproof seepage control project, super-long structural and all kinds of large-scale concrete construction engineering, become and prevent concrete shrinkage rimose effective technology.At present domestic existing swelling agent all is that to belong to the aquation calcium sulphoaluminate be the ettringite type swelling agent of main expansion sources mostly; It has many good qualities on using; But during its aquation to the essential demand of water; Determined it limited to the shrinkage-compensating effect of cement concrete under drying conditions, swelling agent mixes the risk that has increased the dry shrinkage cracking of concrete on the contrary sometimes.Quicklime as a kind of expansive clinker at first in day the present invention and apply; But this expansive clinker that Japan produces is to adopt Wingdale to get through 1400 ℃～1600 ℃ high-temperature calcinations; Be easy to generate the burning quicklime of crystalline structure dense non-porous, the reactive behavior of this burning quicklime is low, the hydration reaction longer duration; And this " prolong and expand " performance might be destroyed the structure of cement concrete, influence concrete weather resistance.It is domestic to quicklime is less relatively as the research of expansive clinker; Patent CN101333083A is also relevant for the report of quicklime as a kind of expansive clinker; But it be with Wingdale and alumina through high temperature calcine jointly preparation with calcium hydroxide and two kinds of hydrated products of ettringite composite expanded grog of quicklime one calcium sulphoaluminate class that is expansion sources, quicklime is not single expansion component.Though the introducing of calcium sulphoaluminate expansion sources has increased the expansion character of expansive clinker; But the essential demand that need combine large quantity of moisture during its aquation; Determined the two expansion sources expansive clinkers of this type to be difficult under the drying conditions of lack of water maintenance, produce effectively and expanded, therefore limited to the shrinkage-compensating effect under the cement concrete drying conditions.In order to reduce the risk of cement concrete shrinkage cracking in dry environment; Developing a kind of can under drying conditions, the generation effectively expands; Basically the early-age shrinkage of full remuneration cement concrete; And can produce demi-inflation, become vast a kind of target of being engaged in the scientific and technical personnel of cement concrete research shunk the new concrete swelling agent that effectively compensates the later stage of cement concrete.
Summary of the invention
The present invention provides a kind of preparation method of calcium oxide expansion agents, and the wet curing of gained swelling agent after to the slurry moulding requires low, cement concrete is produced effectively expand.
Said preparation method of calcium oxide expansion agents is following: said calcium oxide expansion agents is calcined acquisition calcium oxide expansive clinker down at 1100～1300 ℃ after wearing into raw material by Wingdale and composite mineralizer powder mix; Form with dispersed carrier combined grinding again; Said composite mineralizer is that 50%～70% gypsum and 30%～50% copper ashes are formed by mass percentage content; The mass ratio of composite mineralizer and Wingdale is 5: 95～10: 90, and the mass ratio of said calcium oxide expansive clinker and dispersed carrier is 75: 25～90: 10.
Said copper ashes is the slag that produces in the copper metallurgy process, belongs to a kind of, commercially available of non-ferrous metal slag.The mass percentage content of CuO >=75% in the copper ashes preferably.
As preferred version of the present invention, CaO content>=53% in the Wingdale, SO in the gypsum
3Content>=48%, said per-cent are mass percent.
The concrete technology that calcining obtains grog is prior art, and as preferred version, calcination time is 30～120min.Calcining back quenching in air obtains the calcium oxide expansive clinker.
Said dispersed carrier is porous zeolite, flyash or is the mixture that the flyash of 40%～70% porous zeolite and 30%～60% is formed by mass percentage content.As preferably, the porosity of porous zeolite is 30%～40%; The flyash water demand ratio is below 95%, and 45 μ m tail over and are not more than 12%, and loss on ignition is not more than 5%.
Above-mentioned raw material and calcium oxide expansion agents need reach the requirement to grinding fineness of common raw material and swelling agent.As preferred version, the specific surface area of said raw material is 200～400m
2/ kg.The specific surface area of said calcium oxide expansion agents is 150～450m
2/ kg.
The present invention calcines the limestone powder that mixes the part composite mineralizer separately under 1100 ℃～1300 ℃ low relatively temperature; Preparation is the calcium oxide expansive clinker of expansion sources with calcium hydroxide; Again with the common grinding of the dispersed solid support material of part to certain fineness, prepare a kind of calcium oxide expansion agents.This calcium oxide expansion agents calcining temperature is relatively low; Be difficult for making quicklime to produce burn-off phenomenon; And the hydrated product water requirement is little, and expansion performance is high, and rate of expansion is fast; And cement concrete is produced effectively to expand; Basically the early-age shrinkage of full remuneration cement concrete, and the effective expansion energy that under drying conditions, is produced plays compensation preferably to the later stage dry shrinkage of cement concrete, is the effective technology that in actual engineering, is used to reduce cement concrete dry shrinkage cracking risk.
Description of drawings
Fig. 1 mixes the deformation curve in dry environment behind the cement slurry for instance 1 prepared calcium oxide expansion agents CEA-1.
Fig. 2 mixes the deformation curve in dry environment behind the cement slurry for instance 2 prepared calcium oxide expansion agents CEA-2.
Fig. 3 mixes the deformation curve in dry environment behind the cement slurry for instance 3 prepared calcium oxide expansion agents CEA-3.
Fig. 4 mixes the deformation curve in dry environment behind the cement slurry for instance 4 prepared calcium oxide expansion agents CEA-4.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the technical characterictic of a kind of calcium oxide expansion agents of the present invention and preparation method thereof is done further to set forth.
Raw-material chemical ingredients used in the present invention is as shown in table 1, and wherein the porosity of porous zeolite is 35%, and flyash is I level flyash, and the flyash water demand ratio is that 92%, 45 μ m tails over 10%.
Table 1 starting material chemical ingredients (%)
Embodiment one:
With mass ratio is that 90: 10 Wingdale and composite mineralizer mixes after the common grinding of ball mill to fineness is 200m
2The raw material powder of/kg, wherein composite mineralizer is made up of 55% gypsum and 45% copper ashes.Raw material powder behind the grinding 1200 ℃ of down calcinings, and is taken out firing sample quenching in air immediately after being incubated 120min (promptly 1200 ℃ of calcination times down are 120min) under this temperature, being incubated end, make the quicklime expansive clinker.Is specific surface area 300m with quicklime expansive clinker that makes and dispersed solid support material by the common grinding of proportioning to fineness
2/ kg, the mixing quality ratio is 80: 20, wherein dispersed solid support material is a porous zeolite.After the homogenizing it is packed and promptly obtain a kind of cement concrete that can make of the present invention and in dry environment, produce effective expansible calcium oxide expansion agents CEA-1, product meets the requirement of JC476-2001 cement expansive material industry standard.
Embodiment two:
With mass ratio is that 90: 10 Wingdale and composite mineralizer mixes after the common grinding of ball mill to fineness is 200m
2The raw material powder of/kg, wherein composite mineralizer is made up of 50% gypsum and 50% copper ashes.Raw material powder behind the grinding is calcined down at 1250 ℃, and under this temperature, be incubated 80min, insulation is taken out firing sample quenching in air after finishing immediately, makes the quicklime expansive clinker.Is specific surface area 250m with quicklime expansive clinker that makes and dispersed solid support material by the common grinding of proportioning to fineness
2/ kg, the mixing quality ratio is 77: 23, wherein dispersed solid support material is a high-quality I level flyash.After the homogenizing it is packed and promptly obtain a kind of cement concrete that can make of the present invention and in dry environment, produce effective expansible calcium oxide expansion agents CEA-2, product meets the requirement of JC476-2001 cement expansive material industry standard.
Embodiment three:
With mass ratio is that 92: 8 Wingdale and composite mineralizer mixes after the common grinding of ball mill to fineness is 200m
2The raw material powder of/kg, wherein composite mineralizer is made up of 65% gypsum and 35% copper ashes.Raw material powder behind the grinding is calcined down at 1300 ℃, and under this temperature, be incubated 50min, insulation is taken out firing sample quenching in air after finishing immediately, makes the quicklime expansive clinker.Is specific surface area 300m with quicklime expansive clinker that makes and dispersed solid support material by the common grinding of proportioning to fineness
2/ kg, the mixing quality ratio is 85: 15, wherein dispersed solid support material is made up of 60% porous zeolite and 40% high-quality I level flyash.After the homogenizing it is packed and promptly obtain a kind of cement concrete that can make of the present invention and in dry environment, produce effective expansible calcium oxide expansion agents CEA-3, product meets the requirement of JC476-2001 cement expansive material industry standard.
Embodiment four:
With mass ratio is that 95: 5 Wingdale and composite mineralizer mixes after the common grinding of ball mill to fineness is 200m
2The raw material powder of/kg, wherein composite mineralizer is made up of 50% gypsum and 50% copper ashes.Raw material powder behind the grinding is calcined down at 1300 ℃, and under this temperature, be incubated 100min, insulation is taken out firing sample quenching in air after finishing immediately, makes the quicklime expansive clinker.Is specific surface area 250m with quicklime expansive clinker that makes and dispersed solid support material by the common grinding of proportioning to fineness
2/ kg, the mixing quality ratio is 75: 25, wherein dispersed solid support material is made up of 45% porous zeolite and 55% high-quality I level flyash.After the homogenizing it is packed and promptly obtain a kind of cement concrete that can make of the present invention and in dry environment, produce effective expansible calcium oxide expansion agents CEA-4, product meets the requirement of JC476-2001 cement expansive material industry standard.
The PII52.5 silicate cement that adopts the south of the River-little wild water in field mud ltd to produce; Fixedly water-cement ratio is 0.35; Calcium oxide expansion agents CEA-1, CEA-2, CEA-3 and CEA-4 that the present invention is made; And on the market the commonly used impartial quality place of cement of ettringite type swelling agent (hereinafter to be referred as UEA) total amount 8%, the cement paste benchmark appearance of not mixing swelling agent is represented with blank.Behind the specimen molding directly maintenance be (20 ± 1) ℃ in temperature, in the dry shrinkage environment of relative humidity (60 ± 5) %, behind (24 ± 2) h the demoulding and measure just long, the test specimen length that the certain curing age of the pacing amount of going forward side by side is interior.The drying shrinkage deformation rate representes with the linear deformation rate that all wherein the cement paste test specimen has produced dilatational strain under the expression drying conditions, and negative value representes that the cement paste test specimen has produced shrinkage strain under the drying conditions, and test-results is like Fig. 1,2, shown in 3 and 4.The result shows; The cement paste test specimen that mixes the calcium oxide expansion agents that the present invention makes can produce the marked inflation distortion at the early stage of dry maintenance; And the contraction in later stage had significant compensation, and the ettringite type swelling agent (UEA) that often sell in market in the environment of convection drying during maintenance to the shrinkage-compensating poor effect of cement slurry.
In addition with reference to cement expansive material industry standard JC476-2001; Ettringite class swelling agent UEA commonly used on calcium oxide expansion agents CEA-1, CEA-2, CEA-3 and the CEA-4 of gained of the present invention and the market is all replaced 8% of cement total amount with interior quality such as mode of mixing; Comparative study CEA-1, CEA-2, CEA-3, CEA-4 and UEA under restricted condition, the water of cement mortar are supported expansion effect and dry shrinkage suppresses effect, and test-results is seen table 2.
Can find out by table 2; Limited expansion rate when mixing cement mortar specimen water of the present invention and supporting 7d require in the industry standard JC476-2001 0.025; And water is supported behind the 7d when air drying maintenance 21d; Mortar specimen still shows bigger dilatational strain, and has all occurred bigger shrinkage strain during the dry maintenance of the sand-cement slurry blank of mixing the UEA cement mortar specimen accordingly or not mixing swelling agent experience 21d after water is supported 7d.Therefore, the calcium oxide expansion agents that adopts the present invention to make is supported in the environment at water has bigger confined expansion usefulness, and in dehydration exsiccant environment, still has bigger effective expansion.
Table 2
Claims (8)
1. preparation method of calcium oxide expansion agents; It is characterized in that; Said calcium oxide expansion agents is calcined acquisition calcium oxide expansive clinker down at 1100～1300 ℃ after wearing into raw material by Wingdale and composite mineralizer powder mix; Form with dispersed carrier combined grinding again; Said composite mineralizer is that 50%～70% gypsum and 30%～50% copper ashes are formed by mass percentage content, and the mass ratio of composite mineralizer and Wingdale is 5: 95～10: 90, and the mass ratio of said calcium oxide expansive clinker and dispersed carrier is 75: 25～90: 10.
2. preparation method of calcium oxide expansion agents as claimed in claim 1 is characterized in that, calcination time is 30～120min.
3. preparation method of calcium oxide expansion agents as claimed in claim 1 is characterized in that, calcining back quenching in air obtains the calcium oxide expansive clinker.
4. preparation method of calcium oxide expansion agents as claimed in claim 1; It is characterized in that said dispersed carrier is porous zeolite, flyash or is the mixture that the flyash of 40%～70% porous zeolite and 30%～60% is formed by mass percentage content.
5. preparation method of calcium oxide expansion agents as claimed in claim 4 is characterized in that, the porosity of porous zeolite >=30%, flyash water demand ratio are below 95%, and 45 μ m tail over and are not more than 12%, and loss on ignition is not more than 5%.
6. like each described preparation method of calcium oxide expansion agents among the claim 1-5, it is characterized in that the specific surface area of said raw material is 200～400m
2/ kg.
7. like each described preparation method of calcium oxide expansion agents among the claim 1-5, it is characterized in that the specific surface area of said calcium oxide expansion agents is 150～450m
2/ kg.
8. like each described preparation method of calcium oxide expansion agents among the claim 1-5, it is characterized in that CaO content>=53% in the Wingdale, SO in the gypsum
3Content>=48%, CuO content>=75% in the copper ashes, said per-cent are mass percent.
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| CN103964722B (en) * | 2014-05-04 | 2015-12-30 | 苏州市市政工程设计院有限责任公司 | A kind of chemical admixture improving cement expansive material usefulness under restricted condition |
| CN104671687A (en) * | 2015-01-23 | 2015-06-03 | 湖州丰盛新材料有限公司 | Concrete expansive agent and preparation method thereof |
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| CN104671688B (en) * | 2015-02-05 | 2017-01-18 | 江苏苏博特新材料股份有限公司 | Modified calcium oxide expanding clinker as well as preparation method and application thereof |
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| CN104692693B (en) * | 2015-02-05 | 2017-06-20 | 江苏苏博特新材料股份有限公司 | A kind of modified oxidized calcium class expansive clinker, its preparation method and its application |
| CN104671700B (en) * | 2015-02-05 | 2017-11-03 | 江苏苏博特新材料股份有限公司 | A kind of modified oxidized calcium class cement concrete swelling agent and preparation method thereof |
| CN104671694B (en) * | 2015-02-05 | 2017-02-22 | 江苏苏博特新材料股份有限公司 | Modified calcium oxide expanding agent for compensating concrete temperature shrinkage and preparation method thereof |
| CN105000907B (en) * | 2015-08-17 | 2017-05-31 | 泉州惠安长圣生物科技有限公司 | A kind of method of light ceramic wastewater treatment |
| CN109020317A (en) * | 2018-08-14 | 2018-12-18 | 顺裕（龙岩）混凝土有限公司 | A kind of regeneration concrete preparation method that impermeability is strong |
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| CN113929346A (en) * | 2020-06-29 | 2022-01-14 | 江苏苏博特新材料股份有限公司 | Anti-cracking agent adapted to heavy concrete and heavy concrete based on iron ore aggregate |
| CN112723824B (en) * | 2020-12-30 | 2021-12-10 | 重庆鑫科混凝土有限公司 | High-strength high-fluidity concrete and preparation process thereof |
| CN114477829B (en) * | 2022-01-17 | 2022-09-09 | 西安建祥建材科技有限公司 | Multi-component composite reinforced anti-cracking agent for concrete and preparation method thereof |
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2010
- 2010-01-26 CN CN2010101015203A patent/CN101774777B/en active Active
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| JP特开2002-87861A 2002.03.27 |
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